Coated object and process for making the same



estimated.

Patented Apr. '4, 1944 coa'rnp onssc'r ANnrnooEss FOR MAKING 'rnn SAMENew'comb K. Chaney; Moylan. Pm, assignor to The United Gas ImprovementCompany, a cor- H poratlon of Pennsylvania I No prawns.

Application August 19, 1939, Serial No. 291,007

19 Claims. v(o1. 99 -181) application is a continuation in part ofmy'copendlng, application SeriallNumber 174,011,. filed November11,,1937- This invention pertains generally to the coating o of metals.andiparticularlyl to the coating of metals in sheet form. a v t h Theinvention pertains more particularly to the coating. oi sheet metalwhich is1to be ,iabricated ing,,and the like.

Machine operations, suchas the foregoing, are particularly severe uponcoatings or films adhering to the sheet metal, andin many instances, itis extremely diflicult toohtaina formed object with acoating [or systemadequate for the environment to whichth'e finished article is to t besubjected when in use.

To illustrate, many'types 6r fllrn's and-particularly those made fromresinous materials, crack,

check, striate, silk and/or peel ,when subjected j to the foregoingmechanical operations.

Because oi the great economical advantage of l j coatingthe sheetmetalprior to the various form ging operations, the importance or aiilmor film system' whichf will withstand the various formhis operationswithout Another quality oi extreme importance, particularly in the caseof certain uses to which the finished articlesare to be put, istherelative insolubility'and chemical inertness' oi the minor film'system.1 a

An outstanding example of such a use isin the food packaging iield in,which metal cans and metal foil wrappi are extensive u ed.

The term food is employed herein to mean that which is eaten or drunk orabsorbed for nourishment or otherwise, and; includes not only beveragessuch as beer, but substances from which food is prepared, examples 01which are coifee'beans, whether ground or not, and tea leaves.

In the case of cans, for example, economical considerations make itextremely advantageous iniury cannot be over-- can closing machineduring the well known douhie-seaming can sealing operation.

- into obiects by operations which result in drawing; of the metal suchas occurs in stamping,

, ,10 1 bending, die-drawing, threading, turning, punch- For instance,the die-drawing step produces in the c'an,ends not only anglesof verynearly 90 with relatively sharp bends. but also a peripheral portionwhich is curled back upon itself. A film or film system to be successfulmust withstand such and similar metal working operations without peelingor rupturing or otherwise failing in the slightest degree.

Metalcaps are used in large quantity not only on glass bottles but alsoon certain types of metal containers, such as those for holdingbeverages. In many cases, such caps are provided with threads forengaging cooperating threads upon the bottle or other container.

The operation for forming the threads in the metal caps lsextremelysevere.

In the food packaging field it is, of course, ab soluteiy essential thatthe film or film system be not only completely insoluble and chemicallyinert, but also completely incapable of imparting taste or odor to thefood product.

In this connection, it is a well known fact that the ordinary tin liningis unsatisfactory in the case oi certain foods of which grape juice,orange Juice, and beer are outstanding examples.

Some foods develop hydrogen sulfide upon standing which, in turn, reactschemically with the tin lining to form tin sulfide. In case any of theiron is exposed, suchas through cracks, black iron sulfide is formed.

Furthermore, in the food packaging field, the

packaged food stuff, after sealing of the can, is

in many cases, subjected to a sterilization treatment by the applicationof heat. Such treatment,

by reason of the increased temperatures involved, greatly acceleratesany reactions capable of taking place.

Numerous attempts have been made to find a lacquer which might beapplied over or substito, apply thefllm or fllm' system to thesheetmetal while in the flat. Thecanp'arts arethen cut,

shaped and Joined all'in a' manner well known in H the art. Severestressesfare'set up duringthe fi'orming operations; particularly inthecase of thejdie-drawingiot the can" ends. The can ends are againsubjected tose'verejstresses during the as by the seaming can closingoperation," such tuted for the tin coating. Films made with previouslyknown lacquers, as a rule, however, have failed tohave suflicientadhesion and cohesion to resist forming operations, or they have failedto resist reaction with foods, or they have failed in that they haveimparted taste or odor to the This led to the adoption of a procedurewhereby a coating composition having good bonding properties wasemployed as a primer coat for. a top coat having proper food resistingand'taste and odor characteristics, ofwhichthe material knowncommercially as "Vinylite" is an outstandchuck, seaming rolls, andcooperatingparts oi the ing example. Inturn, this presented the furtherlytically polymerized cyclopentadiene employed in my invention aredescribed and claimed in copending application, Serial Number 194,523,filed March 8, 15238 by Samuel G. Trepp, and copending applicationSerial Number 204,786, filed April 28, 1938, by Frank J. Soday.

The following are specific examples of the preparation of the desiredpolymer.

In this connection, many'films and dualfilm "1 systems develop acloudiness during the sterilization step, such cloudiness beinggenerally referred to as blushing. The resulting discoloration is veryundesirable from the standpoint of market appeal, since the averagehousewife looks with great disfavor upon any discoloration of the ln-'-side surface of a can when removing food therefrom.

vIt follows that any film or film system to be suitable must not only becapable of resisting blushing, but must in itself have an acceptableappearance and preferably one suggesting utmost cleanliness. v i

Since films and film systems of the character under consideration arenecessarily extremely thin, the primer coat is preferably one capable ofdirect contact with the food stuff without chemical reaction and withoutimparting taste or odor thereto. Certain substances which mightotherwise be satisfactory as primer coats fail because they are capableof. imparting taste and odor to foodstuffs through the top coat.

In addition to the foregoing, there are certain metals which areextremely diflicult to coat with satisfactorily adhering films or filmsystems of any character. Examples are zinc, zinc jplate, magnesium andmagnesium alloys, such as the material known commercially as ,Dow metal.In fact, practically all previously known resinous coating compositionsfail .to form a' satisfactory bond with these materials. I

In accordance with my invention, single film systems and multiple filmsystems having all of the above desirable properties may be produced byforming (a) said single film system, or (b)the primer coat of a multiplefilm system provided.

the top coat isof a satisfactory character, or (c) the top coat of amultiple film system provided the primer coat is of a satisfactorycharacter, with a liquid coating composition having as a basecyclopentadiene which has been catalytically polymerized in a manner toimpart to it desired properties, and then permitting such films ofpolymerized cyclopentadiene to dry with or without heat.

Generally speaking, the catalytically polymer:

ized cyclopentadiene employed in my liquid coating composition has thefollowing properties. It is soluble in benzene, toluene, chloroform,carbon tetrachloride and high flash naphtha, and

insoluble in alcohol, acetone, ether and water.

For'the purpose of convenience in the claims, these solubilitycharacteristics will be defined by the term benzene-soluble, though itis to be Example 1 1500 pounds of toluene were charged to a smalljacketed, brine cooled kettle provided with an agitator and a brinecooled reflux condenser. 3- pounds of boron trifiuoride-diethyl ethercomplex were then charged, agitation was started, and the kettle waswarmed ,to 35-40 C. After complete mixing, heating was discontinued andthe steam in the jacket replaced with brine.

A previously prepared mixture of 525 pounds of cyclopentadiene and 500pounds of toluene was gradually added from a mixing tank, maintained ata temperature sufliciently low to prevent the volatilization of thecyclopentadiene. The mixture is preferably below room temperature whenit reaches the reaction kettle.

The rate of addition was so regulated that the contents of the reactionkettle were maintained at a temperature between'25-30 C. whilecirculating cooling brine through the jacket.

From 20 to 60 minutes were required for the addition of thecyclopentadiene-toluene mixture depending upon the emciency of thecooling brine: When addition was complete, the brine fiow was cut downso as to keep the temperature above.

25? C but below C. and the product was agitated for an additional 1hours.

5 pounds of water were now added to hydrolyze the catalyst so that thefluorine might later be removed as hydrogen fluoride by the lime.

After 30 minutes further agitation, '75 pounds of milk of lime (Ca(OH)2)were added. The

. a suction filter, and the product pumped through understood that theactual presence of benzene in the solution or in the applied films isnot implied. Preferably, my liquid coating composition has otherdistinctive properties. v.Among these properties is the ability to forma smooth, glassy, highly flexible and extensible and tenaciouslyadhering film upon drying with or without baking.

Methods for preparing benzene-soluble catathe filter. Any type offilter, such as a plate filter press, centrifuge, etc., might beemployed.

The product was a 20% solution of the desired polymer. This solution maybe used as such for application to surfaces, followed by drying in anoxygen-containing atmosphere, such as with baking after suitableevaporation of solvent, or the solution may be concentrated in a vacuumstill of suitable design to give a product containing any desired higherconcentrationofpolycyclopentadiene, if desired.

.In the above example, the particular temperatures chosenare more orless for expediency, but it will be noted that at no time didthetemperature exceed 100 C. or even 80 C. Constant agitationand brinecooling made it possible to prevent local overheating.

Example 2 0.30 cubic centimeter of aluminum chloridediethyl ethercomplex is'added to 60 grams of toluene with thorough agitation to formasuspension, emulsion or solution.

A mixture of 20 grams of cyclopentadiene and 1 h \more, as pointedoutabove trate. i

An example of the formation of a single film follows:

? loosening, or otherwise I 2,345,588 hour, after which 1 cubiccentimeter of water is 5 grams of a suitable filter aid are then added,a

and the mixture filtered.

A filtered solution containing 16.4 grams of polycyclopentadiene is thusobtained.

Generally speaking, any other boron trifluoride-organic solvent complexor aluminum chloride-organic solvent complex might be substituted in theaboveexamples.

In the above specific examples it will be noted that both thecyclopentadiene and the catalyst are-in diluted, form before addition.Furtherdilutedcyclopenta diene is preferably added to diluted catalystrather than. vice versa to aflord a better control of the speed anduniformityof thereaction and of the amountof heat evolved andconsequently the type of polymer produced. The reaction runs smootherandis much more easily controlled on a large scale.

The addition ofwatertohydrolyze the catalystmakes it possible not" onlyto completely remove the activity of the catalyst and .thus stopthereaction at any point, but also to remove the corrosive anddiscoloring acid constituents. of the catalyst by a suitable lyze thecatalyst, although it maybe added later roducts ma be the cause ofserious discoloration. The insoluble reaction products formed during thehydrolysis and neutralization remain behind on the filter leaving ahighly purified filsystem in accordance with myinvention is as a 1 YEsrampleA A 24% solution of the resinin toluene is applied to sheetmetal, such as tin plate, in such quantities that the final resin filmwhether applied to one coat, or several coats with. or withoutintermediate baking, will have a desired thickness, such as, theequivalent of from 4;to 6 milligrams per square inch ofdry baking. f

The coated sheet, after suitable evaporation of solvent, is placed in anoven and heated to a temperature of 350 F. in order to insuresatisfactory drying during which time the film, takesup oxygen from theair without loss of adhesion, fiexibilty or extensibillty. A suitablebaking time is between onequarter of an hour and one and a half hours.The elevated temperatures employed favor the adding on of oxygen.

Sheet metal thus coated is ready for the most drastic formingoperations, such as encountered in the manufacture of cans or othercontainers, bottle caps, screw caps, and the like- It will alkali.Thealkali is preferably added with the water 'used to hydrofilm afterfor a period of minutes.

A tin plated sheet, or other metal sheet, is

' coated with a solution of my resin in toluene, say

of concentration, in sufilcient quantity to f secure a desiredfinalcoating weight, say of apbaking.

proximately 3 milligrams'per square inch after The coated sheet aftersuitable evaporation of solvent is placed in an oven andbaked at atemperature of say 250 V F. for a period of 15 minutes, thepolycyclopentadiene adding on oxygen from the atmosphere during thebaking.

Upon cooling, 2. solution of Vinylite in a mixture of higher boilingketones is applied in suflioient quantity such that the dual film systemwill have a desired thickness after drying of the Vinylite filmlsuch aswith baking, say a thickness equivlaent to"4' to 6 milligrams per drydual ,film. a

.The coated sheet after suitable evaporation of solvent is then rebakedin the same manner as with theprimer coat.

It will be understood, of course, that broadly speaking, the top coat isnot limitedto Vinyl- I ite, which is the co-polyrner of vinyl acetateand vinyl-chloride, but may be a polymer of any ,Of the vinyl compoundsused as raw materials -vinylchloride or vinyl for the several vinylresins; e. -.g.,1vinyl acetate, chloracetate. In fact other types ofresins may, beadapted, for application as the top coat over mycatalytically polymerlzed cyclopentadiene resin.

Vinyl resins suitable for use in forming the top coat of my inventionmaybe formed from vinyl esters by known polymerization processes. The

co-polymerization of polymerization products of inorganic vinyl esters,such as vinyl halides, or those of organic vinyl esters, such as vinylesters of aliphatic acids, may be used. l

I prefer to use vinyl resins resulting from the two, or more vinylesters. For example, vinyl resinshaving desirable properties may beprepared by of a vinyl halide and a vinyl ester of an aliphatic acid. al

Products of the copolymerization of vinyl chloride and vinyl acetate'inproportions ranging from about 10% to 90% by weight of the chloride areparticularly desirable.

The commercial product sold under the trade I name Vinylite falls in thelatter category.

, form flexible top coats which adhere exceptionally well to my primercoat, such top coat (like my primer coat) being odorless and tasteless.

To a certain extent, the characteristics of the preferred vinyl resins.are retained when the vinyl resin is modified by the addition of asecond resin or gum, a cellulose ester, or a high boiling solvent havingplasticizing or softening action on withstand extremely rough treatmentwithout b sterilization treatment. In fact, the coating appears to beimproved during sterilization. An example of the formation of a dual himthe resin. Due to this property, the vinyl resins may be modified tomeet specific requirements without materially altering the chemicalproperties of the resins employed as the top coat.

However, in thefood packaging field, the commercial product sold underthe trade name Vinylite without modification is wellsuited for thepurpose.

This product is thought to result from the cothe co-polymerizationwith15% vinyl acetate. y Since my polycyclopentadiene films not only factoryresults.

- and to heating in the I oxygen-containing gasas a means-of drying mycoating or film,-it is to be understood that the." taking on of oxygenby the film need not necessarily take place simultaneously with theheating or baking. On the contrary,

cellent results by heating'or baking the'coatin'gI or the coated objectin aninert atmosphere as of nitrogen, carbondioxide, or the likefollowed by exposure to the atmosphere or other oxygen I top coating ofpolymerization of about 85% of vinyl "chloridebond well to surfaces butalso are highly resistant to attack by foods, and do not impart taste orodor thereto, they may be-used as top coats over primer coats of othermaterials, if desired. It is, of course, understood that mypolycyclopentadiene resin may be used for both a primer coat and a topcoat or in any othernumber :of coats.

=With respect to the temperatureand time of baking mypolycyclopentadiene films,. I usually 1 its application, or applying thevulcanization agentover the-film after its application, or enclosing theapplied film in an atmosphere of vulcaniz'inggaasuch-as HzS, or anycombination prefer not to exceed about 40091. andat such temperatures abaking time not longer than about minutes to avoid any possible injurytothe if film. *However, in :one experiment I was able tomaintainabaking temperature of 425 .F. for

70 minutes without injury to the film. Thus, although my resin films maybe safely subjected to higher temperatures during. baking, in-general, j

-' of the foregoing; or otherwise. The application of heat hastens thedrying or hardening action.

' Filmsfof excellent character are obtained when theapplied films aredried or hardened using HzS with' the application of heat.

1 "For exampldasolution 'of my resin may con- I find teir peratures upto 350 F. and baking'.'

times up tominutes very satisfactory. With higher temperaturesthe-bakingtime may be shortened to yield similar satisbroadly, l

' atmosphere or other oxygen-containing gas, say

correspondingly While I"'have referred lid-baking presenceof air-' or ancontainingmedium.

I dditional drying or hardening of the film re s suits fromtheabsorption of oxygen.

Similarly, in preparing my multiple-film SYS'? Similar'drying proceduremay be "tain dis'solved, H23 and after its application to 20:

the metalsurface, thefilm maybe dried in an atmosphere of HiSwith theapplication of heat.

' A; baking temperature'of 350--F. and a baking time'of l5 'minute s isillustrative.

' Vulcanizedpolycyclopentadiene films may not be oxygen containing', andmay or may not be capable of'taking up oxygen, if exposed to the at agreatly 'redu ced rate. I

I I applied to the'vinyl top "coat, if desired; I f'Refe'rence is madeto my copending applica- Ihaveobmmed f non Serial'No. 370,138,'fil edDecember 14, 1940.

After-dryingor hardening my polycyclopentadiene films are, generallyspeaking, insoluble.

tems and particularly a system including" my,

I resin film and a Vinylite, film, the drying or hardening of mycyclopentadiene resin film may be secured (a) by baking or heating inanoxygencontaining atmosphere, or (b) baking my'cyclo-i pentadiene resinfilm in an inert atmosphere but permitting it to stand or fseason incontact with an oxygen-containing atmosphere for ag., alweek) beforeapplying the .r Vinylite, or (c)*baking or heat-' 1 ing mycyclopentadiene resin film in an inert film with the top and thenletting the dual period of time (c.

atmosphere, coating the baked coating of Vinylitef I film stand or-season" in contact wth an oxygen-containing atmosphere such as beforeusing the coated article for its intended purpose (in the last-namedcase, oxygen evidently penetrat es or seeps through the top resin filmto mycyclopentadiene resin primer coat), or (d) applying and heating mycyclopentadiene resin film in an inert atmosphere-coating with atop coatfilm, such as Vinylite," still in of another resin an'inert atmosphere,and heating the multiplefilm system thus formed, still in an inertatmos- "While thefilm thicknesses given are found to ='be extremelysuitable for the purpose, and particularlyfor food containers, otherfilm thick-* nesses may-obviously be employed without departingfrom'thespirit of the invention.

While in the above specific examples toluene isused,-it is tobeunderstood that-other suitable solvents may be employed withcorresponding results of which benzene, xylene, ethyl benzene,

naphtha, chloroform and carbon tetrachloride are examples.

While the foregoing particular description has been concerned primarilywith the application of the protective film or films to metal sheets ofa gauge used in the manufacture of tin cans,

"cation Serial No. 491,947,

phere, or"(e) any combination of any of the fore-- going.

- Since the resin coating resulting from (d) wherein the entire seriesof operations take place in an inert atmosphere is entirely satisfactoryfor I vention.-

any well to my primer coat, such top coat like commercial use, mycyclopentadiene resin films either by heat, v

may be. satisfactorily hardened or by an oxygen-containing environmentor by a combination of both. I

it will be obviousfthat my invention is not limited thereto but may beapplied to any metal sheet material, and in fact, to metallic objects ingeneral whether prefabricated or not, where a tough strongly adheringfilm or film system is desired.

Thus, theresin film may be applied to metal.

foil. Reference is made to my copendingapplifiled June 23, 1943. As anillustration, tin foil and aluminum foil, each of whichis used topackage dairy products like butter'and'cheese, may beso coated. Ifdesired, these materials'in molten form may be poured into moldslinedwith foil coated in accordance with my invention.

So too,lead foil, such as is used to package tea leaves; may becoatedinaccordanee with my in- I Metal foil'may be coatedby any desiredprocedure. For example, the foil may be passed through a solution of thecoating material and the-excess removed by means of doctor blades orrolls. Or a'conventional r011 type coating pro- 1 cedure may be employedand the solvent removed and/or recovered in a drying tower.

metal foil may be strengthened by If desired,

rial has completely dried. I V by coating the opposite side of the metalfoil and dryingthe filmfor contact with foodstuffs. On the other hand,metal foilcoated with my dual 7 1 filmsystem with Vin ylite as the topcoat may be hot pressed-against paper or foil to efiect it withpaper,or, by, laminating two or r mclilre foiI -layrs.#-F or example'a sheetof metal t V bejcoated-on one side and the coatedsidepressedintocontactiwith a sheetof paper or second sheet. of foilbeforethe coating mate- This may be followed union of the materials.While the invention has been more particularly described in connectionwith the coating of sheet metal including foilin the flat, my resin filmor film system may be applied during or after any forming operationsforconverting; the initial material into the finished object- It isgenerally useful for coating metallic objects in general,

whether fabricated from sheet metal or not, or whether pre-fabrica'tedin whole or in part prior to application of the, film or film system.

While it is preferred to employ it without additives, the addition ofother substances may be made with consequent modified results, providedthe outstanding characteristicsof thematerial are not substantiallydestroyed. The presence V of apolymerof methyl cyclopentadiene per se ora, co-polymer' or cyclopentadiene and methyl cyclopentadiene, or. both,in amounts up to of the order of from 10 to 20% and possibly more,

- appears to have no deleterious effect. This does not apply to resinousmaterials, in, general and extreme care should-be exercised in makingany J additions.

By the termffhomo-poiymeri is meant the result of the additivecombinationof amonomer and/or polymers of the same. monomer, asdistinguished from aj..co-polymer.. which results from the additivecombination-of different monomers and/or polymers of diflerentmonomers.The presence of up to 20% ormore of methyl cyclopentadiene in thestarting'material of Examples 1 and 2 appears. to have no outstandingdeleterious effect and the resulting polymerized product is definedincertain of the. claims as resinous co-polymer of cyclopentadiene andmethyl cyclopentadiene in which copolymer the proportion of methylcyclopentadiene. does, not exceed 20%. The absence of all othermaterials polymerizable-underthe conditions employed is pre- U ferred.In fact. forth preparation of protec- ..tive films giving the bestresults from every standpoint, itispreferred that there be presentin.:the; starting materials no substantial quancities of; any other,materials (besides the cyclopentadiene and methyl cyclopentadiene) whichwill form a resin under the polymerization conditions prevailing.

My polycyclopentadiene films are naturally colored in beautiful oldgold. If desired, suitable coloring materials may be added such as dyes,pigments, and lakes. The same applies with re- 7 'spect to the Vinylitetop coat. However, in the food packaging field, care should be exercisedwithrespect to any additives so as not to lower or destroy the excellentqualities of the original material for this particularuse.

Since in' the food packaging field the important. consideration is thatthe resin in contact with the" food be chemically inert, insoluble inthe foodstuff, incapable of imparting odor and taste thereto, andstrongly adherent to the enclosing wall, outside portions of thecontainer or foil may be left uncoated, or may be coated changes,omissions, additions. substitutions,

and/or'fmodifications may be made within the scope of the claims withoutdeparting from the spirit of the invention.

I claim:

1. A formed film-coated article shaped by deformation of a metallic bodycoated with dried resinous polymer of cyclopentadiene selected from thegroup consisting of resinous polycyclopentadiene and resinous copolymerof cyclopentadiene and methyl cyclopentadiene in which copolymer theproportion of methyl cyclopentadiene does not exceed 20%, said formedfilm adhering tenaciously to the formed metal.

2. A formed film-coatedarticle shaped by drawing a metallic sheet coatedwith dried resinous polymer of cyclopentadiene selected from the groupconsisting of resinous polycyclopentadiene and resinous copolymer ofcyclopentadiene and methyl cyclopentadiene in which copolymer theproportion of methyl cyclopentadiene does not exceed 20%, said formedfilm adhering tenaciously to the drawn metal.

3. A formed film-coated container cap shaped by drawing film-coatedmetallic sheeting coated with driedv resinous polymer, ,ofcyclopentadiene selected from. the group consisting of resinouspolycyclopentadiene and resinous copolymer of cyclopentadiene and methylcyclopentadiene in which copolymer the proportion of methylcyclopentadiene does not exceed 20%, said formed film which copolymerthe proportion of methyl cyclopentadiene does not exceed 20%, saidformed film adhering tenaciously to the drawn metal ineludingthethreaded portion thereof.

5. A formed film-coate'd'food container shaped by deformation ofmetallic sheeting coated with dried resinous polymerof cyclopentadieneselected from the group consisting of resinous polycyclopentadiene andresinous copolymer of cyclo- .pentadiene and methyl cyclopentadiene inwhich copolymer the proportion of methyl cyclopentadiene does not exceed20%, said formed'film ad-' hering tenaciously to the formed' metal. r

6. A food package comprising formed filmcoated metallic sheeting shapedby deformation of metallic sheeting coated with a primer coat of driedresinous polymer of cyclopentadiene selected from the group consistingof resinous polycyclopentadiene and resinous copolymer ofcyclopentadiene and methyl cyclopentadiene in which copolymer theproportion of methyl cyclopentadiene does not exceed 20%, and a top coatof dried resinous copolymer of vinyl chloride and vinyl acetate, saidpackage for food having at least the surface thereof which wouldotherwise comein contact with the food to be packaged coated with theformed film, said formed film adhering tenaciously to the formedlmetal.

7. A food package comprising formed filmcoated metallic sheeting shapedby deformation of metallic sheeting coated with dried resinous polymerof cyclopentadiene selected "from the, group consisting of resinouspolycyclopentadiene I portion of dried resinous .coat'ed with-a i'ormedprotective layer 1 -thetic resin'which comprises coating metallicmaterial fromwhichthe article is to be formed with resinous polymer ofcyclopentadiene selected pentadiene and methyl cyclopentadiene in vdiene does not exceed 20%,

and resinous copolymer of cyclopentadiene and methyl cyclopentadiene inwhich copolymer the proportion of methyl cyclopentadiene does not exceed"20%,-said food package having at least the surface thereof which bepackaged coated with the formed film, said formed film adhering stronglyto the formed metal.

' with-' resinous polymer "of cyclopentadiene selected 'from' the groupconsisting of resinous'polycyclopentadiene and resinous copolymer ofcy-- clopentadi'enefand methyl cyclopentadiene in which copolymer theproportion of methyl cy- "clopentadie'ne does not exceed 20%, dryingsaid i would otherwise come in contact with the food to 8. A formedfilm-coated article shaped by body coated with an oxidized drawing ametallic formed film adhering tenaresinous film, said coating, applyingover said'first-mentioned coating' a second'coating' of resinouscopolymer of vinyl chloride and vinylacetate, drying saidsecend-mentioned coating','-and subjecting the coated sheeting toshapingoperations to produce said 4 formed article.

ciously to the formed metal and being comprised preponderantly ofoxidized resinous polymer of material containing at least one of a groupconsisting of (a) cyclopentadiene and (b) cyclo- 13. A process -forproducing a formed coated article with a formed protective layer ofsynthetic resin whichcomprises coating metallic material from which thearticle is to be formed with a jsinallproportion of resinous polymethylpentadiene in admixture with up to'20% of methyl cyclopentadiene assubstantially the only resin forming content of said materiaL' 9'. Aformed film-coated article Shaped by drawing a metallic sheet coatedwith a smallpropolym'ethyl cyclopentadiene in admixture with notexceeding 20%. i 10. A process for producing a formed. article oisyncyclope'ntadiene in admixture with resinous polycyclopentadiene saidproportion of polymethyl cyclopentadiene-not exceeding 20%, drying'saiclc0ati'ng,'and subjecting the coated material to i shaping operations toproduce a formed article.

dried-resinous polycyclopentadiene, said formed film adheringtenaciously 'tothe drawn metal, and the proportion of polymethylcyclopentadiene in said admixture H from the group consisting ofresinouspolycyclocyclowhich copolymer the proportion of methylcyclopentadryingsaid coating,

pentadiene'and resinous copolymer of and subjecting the coated materialto shaping operations to produce a; formed article.

1 11. A method for producing a coated can cover having sharplybentcoated-"portlons from-metallic sheeting which comprises coating saidsheeting from which the can cover is to be formed ,withresinous polymerof cyclopentadiene selected from the group consisting, of resinouspolycyclopentadiene and resinous copolymer of cyclepentadiene andmethylcyclopentadiene in which copolymer the proportion of methylcyclopentadiene does not exceed 20%, drying said coating, .cutting ablank of the desired shape from said sheeting, and die-drawing saidcoated blank to the desired can cover shape having said sharply bentportions.

12. A process for article coated with producing a formed metallic I aformed protective layer of i synthetic resin which comprises coatingmetallic t sheeting fromwhich t e article is to be formed 'res'inouspolycyclopentadlene =14. A formed film-coated article shaped bydeformation 'of a metallic body coated with a primer coat of driedresinous polymer of cyclopentadieneselected from the group consisting ofand resinous copolymer oi cyclopentadiene and methyl cyclopentadieneinwhich copolymer the proportion of methyl cyclopentadiene does notexceed 20% and a topcoatof dried-resinous polymerized vinyl ester,saidformedfilm'adhering tenaciously to the *formedmetal; II

:-15.'A formed film-coated article shaped by drawing a metallic sheetcoated with dried resinous polycyclopenta'diene said formed filmadhering tenaciously to the drawn metal.

16. A formed-film-coated can shaped :by drawing a metallic sheet coatedwith dried resinous polycyclopentadiena's'aid formed film adheringtenaciously to the drawn metal.

- 17. A- fcrmed-"film-coated article shaped by drawing tin plate coatedwith dried resinous polycyclopentadiene,said 'formed film adheringtenaciouslyto-the drawnmetal.

18;A formed film-coated article shaped by drawing an iron shet'coatedwith dried resinous polycyclopentadiene; said formed film adheringtenaciously to the drawn metal.

19. A formed film-coated can shaped :by drawing a metallic body coatedwith an oxidized resinous film, sai'd'formed film to the formed metaland adhering tenaciously being comprised preponderantlyof oxidizedresinous polymer of material'contalning cyclopentadiene as substantiallythe only resin forming content thereof.

NEwcoMB K. CHANEY.

